U.S. patent application number 14/611817 was filed with the patent office on 2015-06-04 for water/oil repellent composition and article.
This patent application is currently assigned to ASAHI GLASS COMPANY, LIMITED. The applicant listed for this patent is ASAHI GLASS COMPANY, LIMITED. Invention is credited to Minako SHIMADA, Oomori Yuuichi.
Application Number | 20150152304 14/611817 |
Document ID | / |
Family ID | 50027952 |
Filed Date | 2015-06-04 |
United States Patent
Application |
20150152304 |
Kind Code |
A1 |
SHIMADA; Minako ; et
al. |
June 4, 2015 |
WATER/OIL REPELLENT COMPOSITION AND ARTICLE
Abstract
It is possible to obtain a porous substrate having a water/oil
repellent-treated surface and a moisture-permeable waterproofing
film, which has favorable water/oil repellency and wash durability,
through which penetration of a coating liquid for formation of the
moisture-permeable waterproofing film is suppressed, and from which
peeling of the moisture-permeable waterproofing film is suppressed.
A water/oil repellent composition comprising a copolymer (A) having
from 60 to 95 mass % of units based on a monomer having a R.sup.F
group having at most 6 carbon atoms and from 5 to 40 mass % of
units based on vinylidene chloride, a copolymer (B) having from 50
to 95 mass % of units based on a halogenated olefin and from 5 to
50 mass % of units based on a monomer having a crosslinkable
functional group, and a medium (C), wherein the proportion of the
copolymer (A) is from 70 to 90 mass %, and the proportion of the
copolymer (B) is from 10 to 30 mass %.
Inventors: |
SHIMADA; Minako; (Tokyo,
JP) ; Yuuichi; Oomori; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ASAHI GLASS COMPANY, LIMITED |
Chiyoda-ku |
|
JP |
|
|
Assignee: |
ASAHI GLASS COMPANY,
LIMITED
Chiyoda-ku
JP
|
Family ID: |
50027952 |
Appl. No.: |
14/611817 |
Filed: |
February 2, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2013/070512 |
Jul 29, 2013 |
|
|
|
14611817 |
|
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Current U.S.
Class: |
442/71 ; 427/209;
428/304.4; 523/437; 524/520 |
Current CPC
Class: |
D06M 15/273 20130101;
C09D 133/16 20130101; Y10T 428/249953 20150401; C09D 133/16
20130101; D06M 15/248 20130101; D06M 15/256 20130101; C09D 127/08
20130101; D06M 15/285 20130101; D06M 15/3568 20130101; C08L 2205/02
20130101; D06M 15/267 20130101; D06M 23/10 20130101; D06M 15/277
20130101; D06M 15/3562 20130101; D06M 15/564 20130101; C09K 3/18
20130101; D06M 15/263 20130101; Y10T 442/2098 20150401; C09D 127/08
20130101; D06M 15/353 20130101; C08L 27/06 20130101; D06M 15/3335
20130101; D06M 2200/11 20130101; D06M 2200/12 20130101; D06M 15/29
20130101; C08L 33/06 20130101 |
International
Class: |
C09K 3/18 20060101
C09K003/18; D06M 15/564 20060101 D06M015/564; D06M 15/256 20060101
D06M015/256 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 1, 2012 |
JP |
2012-171133 |
Claims
1. A water/oil repellent composition which comprises a copolymer
(A) having from 60 to 95 mass % of units based on the following
monomer (a1) and from 5 to 40 mass % of units based on the
following monomer (a2), a copolymer (B) having from 50 to 95 mass %
of units based on the following monomer (b1) and from 5 to 50 mass
% of units based on the following monomer (b2), and a medium (C),
wherein the proportion of the copolymer (A) is from 70 to 90 mass
%, and the proportion of the copolymer (B) is from 10 to 30 mass %
relative to the total amount (100 mass %) of the copolymer (A) and
the copolymer (B): monomer (a1): a compound represented by the
following formula (1): (Z--Y).sub.nX (1) wherein Z is a C.sub.1-6
polyfluoroalkyl group or a group represented by the following
formula (2), Y is a bivalent organic group having no fluorine atom,
or a single bond, n is 1 or 2, and X is, when n is 1, any one of
the groups represented by the following formulae (3-1) to (3-5)
and, when n is 2, any one of the groups represented by the
following formulae (4-1) to (4-4):
C.sub.iF.sub.2i+1O(CFX.sup.1CF.sub.2O).sub.jCFX.sup.2-- (2) wherein
i is an integer of from 1 to 6, j is an integer of from 0 to 10,
and each of X.sup.1 and X.sup.2 is a fluorine atom or a
trifluoromethyl group; --CR.sup.2.dbd.CH.sub.2 (3-1)
--C(O)OCR.sup.2.dbd.CH.sub.2 (3-2) --OC(O)CR.sup.2.dbd.CH.sub.2
(3-3) --OCH.sub.2-.phi.-CR.sup.2.dbd.CH.sub.2 (3-4)
--OCH.dbd.CH.sub.2 (3-5) wherein R.sup.2 is a hydrogen atom, a
methyl group or a halogen atom, and .phi. is a phenylene group;
--CH[--(CH.sub.2).sub.mCR.sup.3.dbd.CH.sub.2]-- (4-1)
--CH[--(CH.sub.2).sub.mC(O)OCR.sup.3.dbd.CH.sub.2]-- (4-2)
--CH[--(CH.sub.2).sub.mOC(O)CR.sup.3.dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4) where R.sup.3 is a hydrogen atom, a
methyl group or a halogen atom, and m is an integer of from 0 to 4;
monomer (a2): vinylidene chloride; monomer (b1): a halogenated
olefin; and monomer (b2): a monomer having no polyfluoroalkyl group
and having a crosslinkable functional group.
2. The water/oil repellent composition according to claim 1,
wherein Z is a C.sub.4-6 perfluoroalkyl group.
3. The water/oil repellent composition according to claim 1,
wherein Y is a C.sub.2-4 alkylene group, n is 1, and X is a group
represented by the formula (3-3).
4. The water/oil repellent composition according to claim 1,
wherein the copolymer (A) further has units based on the following
monomer (a3): monomer (a3): a monomer having no polyfluoroalkyl
group and having a crosslinkable functional group.
5. The water/oil repellent composition according to claim 4,
wherein the crosslinkable functional group in the monomer (a3) is a
hydroxyl group, a blocked isocyanate group, an amino group, a
N-hydroxymethylamide group, an epoxy group or a carboxy group.
6. The water/oil repellent composition according to claim 4,
wherein the copolymer (A) has from 65 to 89.9 mass % of the units
based on the monomer (a1), from 10 to 34.9 mass % of the units
based on the monomer (a2) and from 0.1 to 25 mass % of the units
based on the monomer (a3).
7. The water/oil repellent composition according to claim 1,
wherein the monomer (b1) is vinyl chloride.
8. The water/oil repellent composition according to claim 1,
wherein the copolymer (B) further has units based on a monomer (b3)
which is a monomer other than the monomer (b1) and the monomer
(b2).
9. The water/oil repellent composition according to claim 8,
wherein the monomer (b3) is the monomer (a1) or a monomer having a
C.sub.1-22 alkyl group.
10. The water/oil repellent composition according to claim 8,
wherein the proportion of the units based on the monomer (b3) is
from 2 to 40 mass % relative to the units (100 mass %) based on all
the monomers in the copolymer (B).
11. An article having a porous substrate, wherein the porous
substrate has a water/oil repellent-treated surface treated with
the water/oil repellent composition as defined in claim 1 on at
least one side, and has a moisture-permeable waterproofing film on
one side.
12. The article according to claim 11, wherein the porous substrate
is cloth.
13. A method for producing a porous substrate having a water/oil
repellent-treated surface and a moisture-permeable waterproofing
film, which comprises treating at least one side of a porous
substrate with the water/oil repellent composition as defined in
claim 1 to form the water/oil repellent-treated surface and then
applying a coating liquid containing a material of the
moisture-permeable waterproofing film to one side of the porous
substrate to form the moisture-permeable waterproofing film.
Description
TECHNICAL FIELD
[0001] The present invention relates to a water/oil repellent
composition, and an article having its surface treated with the
water/oil repellent composition.
BACKGROUND ART
[0002] As a method for imparting water/oil repellency to the
surface of a substrate such as cloth, a method of treating the
substrate with a water/oil repellent composition composed of an
emulsion having, dispersed in an aqueous medium, a copolymer having
units based on a monomer having a polyfluoroalkyl group
(hereinafter a polyfluoroalkyl group will be referred to as a
R.sup.f group) having at least 8 carbon atoms has been known.
[0003] However, recently, EPA (US Environmental Protection Agency)
has pointed out that a compound having a perfluoroalkyl group
(hereinafter a perfluoroalkyl group will be referred to as a
R.sup.F group) having at least 7 carbon atoms is likely to be
decomposed in the environment or in the body, and the decomposition
product is likely to be accumulated, i.e. it presents a high
environmental impact. Therefore, a water/oil repellent composition
comprising a copolymer which has units based on a monomer having a
R.sup.F group having at most 6 carbon atoms, and has no units based
on a monomer having a R.sup.F group having at least 7 carbon atoms,
has been required.
[0004] As a water/oil repellent composition comprising such a
copolymer, for example, the following water/oil repellent
compositions (1) and (2) have been proposed.
[0005] (1) A water/oil repellent composition comprising a copolymer
having units based on the following monomer (a), units based on the
following monomer (b) and units based on the following monomer (c),
and a medium, wherein the molar ratio ((b)/(c)) of the units based
on the monomer (b) to the units based on the monomer (c) is at
least 1 (Patent Document 1).
[0006] Monomer (.alpha.): a monomer having a R.sup.F group having
at most 6 carbon atoms.
[0007] Monomer (b): vinyl chloride.
[0008] Monomer (c): a vinyl ether having no R.sup.f group and
having a crosslinkable functional group.
[0009] (2) A water/oil repellent composition comprising a copolymer
having units based on the following monomer (.alpha.) and units
based on the following monomer (.beta.) and as the case requires,
units based on the following monomer (.gamma.), and having a mass
average molecular weight of at least 40,000, and a medium (Patent
Document 2).
[0010] Monomer (.alpha.): a monomer having a R.sup.F group having
at most 6 carbon atoms.
[0011] Monomer (.beta.): vinylidene chloride.
[0012] Monomer (.gamma.): a monomer having no R.sup.f group and
having a crosslinkable functional group.
[0013] A fiber product comprising e.g. fabric the surface of which
is treated with the water/oil repellent composition (1) or (2) is
considered to have favorable water repellency after it is washed
and dried without forcible heating (hereinafter referred to as wash
durability).
[0014] By the way, an article having its surface treated with a
water/oil repellent composition (a fiber product such as a sports
wear), a moisture-permeable waterproofing film may be formed on the
rear side so as to impart a function to release water vapor by
sweating from the body and a function to prevent penetration of
rain (Patent Document 3). As a method for producing fabric having
such a moisture-permeable waterproofing film, a laminate method or
a coating method is well known.
[0015] The laminate method is a method of bonding a porous
polyfluoroethylene film or a microporous polyurethane resin film to
the rear side of fabric treated with a water/oil repellent
composition by means of an adhesive component or the like. The
coating method is a method of applying a coating liquid containing
a polyurethane resin, an acrylic resin or the like to the rear side
of fabric treated with a water/oil repellent composition. For the
fabric, it is required that the bonded or applied resin film is not
easily peeled.
[0016] Further, as a medium contained in the coating liquid, in the
case of dry coating of forming a resin film by drying after
application, a highly volatile solvent such as methyl ethyl ketone,
ethyl acetate, toluene or isopropyl alcohol is used. Whereas, in
the case of wet coating of forming a resin film by solidification
in water, a polar organic solvent such as N,N-dimethylformamide
(hereinafter referred to as DMF) is used.
PRIOR ART DOCUMENTS
Patent Documents
[0017] Patent Document 1: WO2010/047258 [0018] Patent Document 2:
WO2010/123042 [0019] Patent Document 3: JP-A-07-229070
DISCLOSURE OF INVENTION
Technical Problem
[0020] However, if a coating liquid is applied to the rear side of
fabric treated with the water/oil repellent composition (1) to form
a moisture-permeable waterproofing film, the coating liquid
penetrates to the front surface side of the fabric, and a resin
film is formed even on the front surface side of the fabric, thus
impairing the design of the article.
[0021] On the other hand, if a coating liquid is applied to the
rear side of fabric having its surface treated with the water/oil
repellent composition (2) to form a moisture-permeable
waterproofing film, penetration of the coating liquid to the front
surface side of the fabric is inhibited. However, the adhesion
between the fabric having its surface treated with the water/oil
repellent composition (2) and the moisture-permeable waterproofing
film is insufficient, and the moisture-permeable waterproofing film
is likely to be peeled off.
[0022] The object of the present invention is to provide a
water/oil repellent composition from which an article can be
obtained, which has favorable water/oil repellency and wash
durability, through which penetration of a coating liquid for
formation of a moisture-permeable waterproofing film can be
suppressed, and from which the moisture-permeable waterproofing
film is suppressed, and which the article presents a low
environmental impact, and an article comprising a porous substrate
such as cloth, the surface of which is treated with the water/oil
repellent composition.
Solution to Problem
[0023] The water/oil repellent composition of the present invention
comprises a copolymer (A) having from 60 to 95 mass % of units
based on the following monomer (a1) and from 5 to 40 mass % of
units based on the following monomer (a2),
[0024] a copolymer (B) having from 50 to 95 mass % of units based
on the following monomer (b1) and from 5 to 50 mass % of units
based on the following monomer (b2), and
[0025] a medium (C),
wherein the proportion of the copolymer (A) is from 70 to 90 mass
%, and the proportion of the copolymer (B) is from 10 to 30 mass %
relative to the total amount (100 mass %) of the copolymer (A) and
the copolymer (B):
[0026] monomer (a1): a compound represented by the following
formula (1):
(Z--Y).sub.nX (1)
wherein Z is a C.sub.1-6 polyfluoroalkyl group or a group
represented by the following formula (2), Y is a bivalent organic
group having no fluorine atom, or a single bond, n is 1 or 2, and X
is, when n is 1, any one of the groups represented by the following
formulae (3-1) to (3-5) and, when n is 2, any one of the groups
represented by the following formulae (4-1) to (4-4):
C.sub.iF.sub.2i+1O(CFX.sup.1CF.sub.2O).sub.jCFX.sup.2-- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0
to 10, and each of X.sup.1 and X.sup.2 is a fluorine atom or a
trifluoromethyl group;
--CR.sup.2.dbd.CH.sub.2 (3-1)
--C(O)OCR.sup.2.dbd.CH.sub.2 (3-2)
--OC(O)CR.sup.2.dbd.CH.sub.2 (3-3)
--OCH.sub.2-.phi.-CR.sup.2.dbd.CH.sub.2 (3-4)
--OCH.dbd.CH.sub.2 (3-5)
wherein R.sup.2 is a hydrogen atom, a methyl group or a halogen
atom, and .phi. is a phenylene group;
--CH[--(CH.sub.2).sub.mCR.sup.3.dbd.CH.sub.2]-- (4-1)
--CH[--(CH.sub.2).sub.mC(O)OCR.sup.3.dbd.CH.sub.2]-- (4-2)
--CH[--(CH.sub.2).sub.mOC(O)CR.sup.3.dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4)
where R.sup.3 is a hydrogen atom, a methyl group or a halogen atom,
and m is an integer of from 0 to 4;
[0027] monomer (a2): vinylidene chloride;
[0028] monomer (b1): a halogenated olefin; and
[0029] monomer (b2): a monomer having no polyfluoroalkyl group and
having a crosslinkable functional group.
[0030] It is preferred that Z is a C.sub.4-6 perfluoroalkyl
group.
[0031] It is preferred that Y is a C.sub.2-4 alkylene group, n is 1
and X is the group represented by the formula (3-3).
[0032] Further, the copolymer (A) preferably further has units
based on the following monomer (a3), and the crosslinkable
functional group in the monomer (a3) is preferably a hydroxy group,
a blocked isocyanate group, an amino group, an N-hydroxymethylamide
group, an epoxy group or a carboxy group.
[0033] monomer (a3): a monomer having no polyfluoroalkyl group and
having a crosslinkable functional group.
[0034] It is preferred that the copolymer (A) has from 65 to 89.9
mass % of the units based on the monomer (a1), from 10 to 34.9 mass
% of the units based on the monomer (a2) and from 0.1 to 25 mass %
of the units based on the monomer (a3).
[0035] The monomer (b1) is preferably vinyl chloride.
[0036] The copolymer (B) preferably further has units based on a
monomer (b3) which is a monomer other than the monomer (b1) and the
monomer (b2), and the monomer (b3) is preferably the monomer (a1)
or a monomer having a C.sub.1-22 alkyl group. The proportion of the
units based on the monomer (b3) is preferably from 2 to 40 mass %
relative to units (100 mass %) based on all the monomers in the
copolymer (B).
[0037] The present invention further provides an article having a
porous substrate, wherein the porous substrate has a water/oil
repellent-treated surface treated with the water/oil repellent
composition on at least one side, and has a moisture-permeable
waterproofing film on one side. The porous substrate is preferably
cloth.
[0038] The present invention further provides a method for
producing a porous substrate having a water/oil repellent-treated
surface and a moisture-permeable waterproofing film, which
comprises treating at least one side of a porous substrate with the
water/oil repellent composition to form the water/oil
repellent-treated surface and then applying a coating liquid
containing a material of the moisture-permeable waterproofing film
to one side of the porous substrate to form the moisture-permeable
waterproofing film.
Advantageous Effects of Invention
[0039] According to the water/oil repellent composition of the
present invention, it is possible to obtain a porous substrate such
as fabric, which has favorable water/oil repellency and wash
durability, through which penetration of a coating liquid for
formation of a moisture-permeable waterproofing film is suppressed,
and from which peeling of the moisture-permeable waterproofing film
is suppressed. Further, the water/oil repellent composition of the
present invention presents a low environmental impact.
[0040] The article having the above treated porous substrate of the
present invention has favorable water/oil repellency and wash
durability, the article is excellent in the design since
penetration of a coating liquid for formation of a
moisture-permeable waterproofing film is suppressed, the
moisture-permeable waterproofing film is hardly peeled from the
article, and the article presents a low environmental impact.
DESCRIPTION OF EMBODIMENTS
[0041] In this specification, a compound represented by the formula
(1) will be referred to as a compound (1). Compounds represented by
other formulae will also be referred to in the same manner.
[0042] Further, in this specification, a group represented by the
formula (2) will be referred to as a group (2). Groups represented
by other formulae will also be referred to in the same manner.
[0043] A (meth)acrylate in this specification means an acrylate or
a methacrylate.
[0044] In this specification, a monomer means a compound having a
polymerizable unsaturated group.
[0045] In this specification, a R.sup.f group is a group having
some or all of hydrogen atoms in an alkyl group substituted by
fluorine atoms, and a R.sup.F group is a group having all the
hydrogen atoms in an alkyl group substituted by fluorine atoms.
[0046] In this specification, among substrates to be water/oil
repellent-treated with the water/oil repellent composition, a
substrate which is porous will be referred to as a porous
substrate. A representative example of the porous substrate is a
sheet-form porous substrate such as cloth.
[0047] In this specification, a moiety derived from a monomer
constituting a polymer will be referred to as "units based on a
monomer" or "monomer units". Units based on a monomer may sometimes
be represented by the name of the monomer and "units".
[0048] The proportion of monomer units in a copolymer in the
present invention is obtained from NMR analysis and elemental
analysis. In a case where it cannot be determined from the NMR
analysis and the elemental analysis, it may be calculated based on
the amount of monomers charged at the time of preparation of the
copolymer.
[0049] The mass average molecular weight (Mw) and the number
average molecular weight (Mn) of a copolymer are molecular weights
as calculated as polystyrene, measured by gel permeation
chromatography (GPC), and specifically, measured by the following
method.
[0050] A copolymer is dissolved in a solvent mixture of a
fluorinated solvent (AK-225 manufactured by Asahi Glass Company,
Limited)/tetrahydrofuran (THF)=6/4 (volume ratio) to prepare a 0.5
mass % solution, which is passed through a 0.2 .mu.m filter to
prepare a sample for analysis. With respect to the sample, the
number average molecular weight (Mn) and the mass average molecular
weight (Mw) are measured under the following conditions.
[0051] Measurement temperature: 37.degree. C.,
[0052] injected amount: 50 .mu.L,
[0053] outflow rate: 1 mL/min,
[0054] eluent: a solvent mixture of a fluorinated solvent (AK-225
manufactured by Asahi Glass Company, Limited)/THF=6/4 (volume
ratio).
<Water/Oil Repellent Composition>
[0055] The water/oil repellent composition of the present invention
comprises a specific copolymer (A), a specific copolymer (B) and a
medium (C) as essential components, and as the case requires,
contains a surfactant (D) and additives (E).
(Copolymer (A))
[0056] The copolymer (A) has units based on the monomer (a1) and
units based on the monomer (a2).
[0057] The copolymer (A) preferably further has units based on the
monomer (a3) and as the case requires, may have units based on the
after-mentioned monomer (a4).
Monomer (a1):
[0058] The monomer (a) is a compound (1):
(Z--Y).sub.nX (1)
wherein Z is a C.sub.1-6 R.sup.f group (provided that the R.sup.f
group may contain an etheric oxygen atom) or a group (2):
C.sub.iF.sub.2i+1O(CFX.sup.1CF.sub.2O).sub.jCFX.sup.2-- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0
to 10, each of X.sup.1 and X.sup.2 which are independent of each
other, is a fluorine atom or a trifluoromethyl group.
[0059] The R.sup.f group is preferably a R.sup.F group. The R.sup.f
group may be linear or may be branched, and is preferably linear.
The R.sup.f group is particularly preferably a C.sub.4-6 linear
R.sup.F group.
[0060] Z may be the following groups.
[0061] F(CF.sub.2).sub.4--, F(CF.sub.2).sub.5--,
F(CF.sub.2).sub.6--, (CF.sub.3).sub.2CF(CF.sub.2).sub.2--,
C.sub.kF.sub.2k+1O[CF(CF.sub.3)CF.sub.2O].sub.h--CF(CF.sub.3)--,
etc., wherein k is an integer of from 1 to 6, and h is an integer
of from 0 to 10.
[0062] Y is a bivalent organic group having no fluorine atom, or a
single bond.
[0063] The bivalent organic group is preferably an alkylene group.
The alkylene group may be linear or branched, and preferably has 1
to 6 carbon atoms. The bivalent organic group may be an organic
group having --O--, --NH--, --CO--, --S--, --SO.sub.2--,
--CD.sup.1=CD.sup.2- (wherein each of D.sup.1 and D.sup.2 which are
independent of each other, is a hydrogen atom or a methyl group),
etc. Particularly preferred as Y is a C.sub.2-4 linear alkylene
group.
[0064] Y may, for example, be the following groups.
[0065] --CH.sub.2--, --CH.sub.2CH.sub.2--, --(CH.sub.2).sub.3--,
--CH.sub.2CH.sub.2CH(CH.sub.3)--, --CH.dbd.CH--CH.sub.2--,
--S--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--SO.sub.2--CH.sub.2CH.sub.2--,
--W--OC(O)NH--V--NHC(O)O--(C.sub.pH.sub.2p)--, etc., wherein p is
an integer of from 2 to 30.
[0066] V is a symmetric alkylene group having no branch, an arylene
group or an aralkylene group and is preferably --C.sub.6H.sub.12--,
-.phi.--CH.sub.2-.phi.- or -.phi.- (wherein .phi. is a phenylene
group).
[0067] W is any one of the following groups.
[0068] --SO.sub.2N(R.sup.1)--C.sub.dH.sub.2d--,
--CONHC.sub.dH.sub.2d--, --C.sub.qH.sub.2q--
wherein R.sup.1 is a hydrogen atom or a C.sub.1-4 alkyl group, d is
an integer of from 2 to 8, and q is an integer of from 1 to 20.
[0069] n is 1 or 2. n is preferably 1.
[0070] X is, when n is 1, any one of groups (3-1) to (3-5) and when
n is 2, any one of groups (4-1) to (4-4):
--CR.sup.2.dbd.CH.sub.2 (3-1)
--C(O)OCR.sup.2.dbd.CH.sub.2 (3-2)
--OC(O)CR.sup.2.dbd.CH.sub.2 (3-3)
--OCH.sub.2-.phi.-CR.sup.2.dbd.CH.sub.2 (3-4)
--OCH.dbd.CH.sub.2 (3-5)
wherein R.sup.2 is a hydrogen atom, a methyl group or a halogen
atom, and .phi. is a phenylene group.
[0071] When n is 1, X is preferably the group (3-3).
--CH[--(CH.sub.2).sub.mCR.sup.3.dbd.CH.sub.2]-- (4-1)
--CH[--(CH.sub.2).sub.mC(O)OCR.sup.3.dbd.CH.sub.2]-- (4-2)
--CH[--(CH.sub.2).sub.mOC(O)CR.sup.3.dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4)
wherein R.sup.3 is a hydrogen atom, a methyl group or a halogen
atom, and m is an integer of from 0 to 4.
[0072] When n is 2, X is preferably the group (4-3).
[0073] The compound (1) is preferably a (meth)acrylate having a
C.sub.4-6 R.sup.F group from the viewpoint of e.g. the
polymerizability with other monomers, the flexibility of the
coating film containing the copolymer (A), the adhesion of the
copolymer (A) to the substrate, the dispersibility in the medium
(C) and efficiency of the emulsion polymerization.
[0074] The compound (1) is preferably a compound wherein Z is a
C.sub.4-6 R.sup.F group, Y is a C.sub.1-4 alkylene group, n is 1,
and X is the group (3-3).
Monomer (a2):
[0075] The monomer (a2) is vinylidene chloride.
[0076] By having the monomer (a2) units, the affinity of the
copolymer (A) to the substrate and the film-forming property are
improved. Therefore, even when a substrate dipped in the water/oil
repellent composition is air-dried, the copolymer (A) will
infiltrate even into a portion where a coating film of the
copolymer (A) is hardly formed, such as a portion between fibers in
fabric, in every hole and corner, and a uniform and ideal coating
film of the copolymer (A) can be formed. As a result, sufficient
wash durability can be imparted to an article.
Monomer (a3):
[0077] The monomer (a3) is a monomer having no R.sup.f group and
having a crosslinkable functional group.
[0078] By having the monomer (a3) units, peeling of the
moisture-permeable waterproofing film can be suppressed, and
further, wash durability of the article will further be
improved.
[0079] The crosslinkable functional group is preferably a
functional group having at least one bond selected from a covalent
bond, an ionic bond and a hydrogen bond, or a functional group
capable of forming a crosslinked structure by an interaction of
such a bond. Otherwise, the crosslinkable functional group may be a
functional group having an active organic group or an element such
as hydrogen or halogen in its molecule.
[0080] Such a functional group is preferably a hydroxy group, an
isocyanate group, a blocked isocyanate group, an alkoxysilyl group,
an amino group, a N-hydroxymethylamide group, a N-alkoxymethylamide
group, a silanol group, an ammonium group, an amide group, an epoxy
group, an oxazoline group, a carboxy group, an alkenyl group, a
sulfonic group or the like, particularly preferably a hydroxy
group, a blocked isocyanate group, an amino group, a
N-hydroxymethylamide group, an epoxy group or a carboxy group,
which is reactive with an isocyanate group of a urethane resin
constituting the moisture-permeable waterproofing film or an amino
group or an isocyanate group of the after-mentioned thermosetting
agent directly or by means of another compound (such as water).
[0081] The monomer (a3) is preferably a (meth)acrylate, an
acrylamide, a vinyl ether or a vinyl ester.
[0082] The monomer (a3) may, for example, be the following
compounds.
[0083] (Meth)acrylates: glycidyl(meth)acrylate,
2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
4-hydroxybutyl(meth)acrylate,
3-chloro-2-hydroxypropyl(meth)acrylate,
dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,
dimethylaminopropyl(meth)acrylate, a polycaprolactone ester of
hydroxyethyl(meth)acrylate (tradename: "PLACCEL", FA, FM series
manufactured by Daicel Chemical Industries, Ltd.,
2-isocyanatoethyl(meth)acrylate, 3-isocyanatopropyl(meth)acrylate,
4-isocyanatobutyl(meth)acrylate, a 2-butanoneoxime adduct of
2-isocyanatoethyl(meth)acrylate, a pyrazole adduct of
2-isocyanatoethyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of
2-isocyanatoethyl(meth)acrylate, a 3-methylpyrazole adduct of
2-isocyanatoethyl(meth)acrylate, an .epsilon.-caprolactam adduct of
2-isocyanatoethyl(meth)acrylate, a 2-butanoneoxime adduct of
3-isocyanatopropyl(meth)acrylate, a pyrazole adduct of
3-isocyanatopropyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of
3-isocyanatopropyl(meth)acrylate, a 3-methylpyrazole adduct of
3-isocyanatopropyl(meth)acrylate, an .epsilon.-caprolactam adduct
of 3-isocyanatopropyl(meth)acrylate, a 2-butanoneoxime adduct of
4-isocyanatobutyl(meth)acrylate, a pyrazole adduct of
4-isocyanatobutyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of
4-isocyanatobutyl(meth)acrylate, a 3-methylpyrazole adduct of
4-isocyanatobutyl(meth)acrylate, an .epsilon.-caprolactam adduct of
4-isocyanatobutyl(meth)acrylate.
[0084] Acrylamides: (meth)acrylamide, N-methyl(meth)acrylamide,
N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide,
methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide,
butoxymethyl(meth)acrylamide, diacetone(meth)acrylamide.
[0085] 3-Methacryloyloxypropyltrimethoxysilane,
trimethoxyvinylsilane, vinyltrimethoxysilane.
[0086] (Meth)acryloyloxyethyltrimethylammonium chloride,
(meth)acryloyloxypropyltrimethylammonium chloride,
(meth)acrylamideethyltrimethylammonium chloride,
(meth)acrylamidepropyltrimethylammonium chloride.
[0087] Vinyl ethers: 2-chloroethyl vinyl ether, 2-hydroxyethyl
vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl
ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether,
4-hydroxycyclohexyl vinyl ether, hexamethylene glycol monovinyl
ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol
monovinyl ether, triethylene glycol monovinyl ether, dipropylene
glycol monovinyl ether, glycidyl vinyl ether, 2-aminoethyl vinyl
ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, allyl
vinyl ether.
[0088] The monomer (a3) is preferably a (meth)acrylate or an
acrylamide, and is specifically preferably a 3,5-dimethylpyrazole
adduct of 2-isocyanatoethyl(meth)acrylate, a 2-butanoneoxime adduct
of 2-isocyanatoethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
N-methylol(meth)acrylamide, glycidyl(meth)acrylate,
3-chloro-2-hydroxypropyl methacrylate, a polycaprolactone ester of
hydroxyethyl(meth)acrylate (tradename: "PLACCEL" FA, FM-series
manufactured by Daicel Chemical Industries, Ltd.).
Monomer (a4):
[0089] The monomer (a4) is another monomer excluding the monomer
(a1), the monomer (a2) and the monomer (a3).
[0090] The monomer (a4) is preferably a (meth)acrylate or an
unsaturated carboxylic acid ester. The (meth)acrylate is preferably
an alkyl(meth)acrylate having a C.sub.1-2 alkyl group, or a
monocyclic or polycyclic cycloalkyl(meth)acrylate having a
C.sub.5-16 cycloalkyl group. The unsaturated carboxylic acid ester
is preferably an unsaturated monocarboxylic acid monoalkyl ester
having a C.sub.1-12 alkyl group or an unsaturated dicarboxylic acid
dialkyl ester. Including other compounds, the monomer (a4) may, for
example, be the following compounds.
[0091] (Meth)acrylates: methyl(meth)acrylate, ethyl(meth)acrylate,
propyl(meth)acrylate, n-butyl(meth)acrylate, t-butyl(meth)acrylate,
i-butyl(meth)acrylate, cyclohexyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, n-hexyl(meth)acrylate,
benzyl(meth)acrylate, octyl(meth)acrylate, lauryl(meth)acrylate,
cetyl(meth)acrylate, stearyl(meth)acrylate, behenyl(meth)acrylate,
isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate,
dicyclopentenyl(meth)acrylate, a (meth)acrylate having a repeating
structure of siloxane bonds in its side chains, a (meth)acrylate
having a urethane bond.
[0092] Unsaturated carboxylic acid esters: crotonic acid alkyl
esters, maleic acid alkyl esters such as diethyl maleate, dipropyl
maleate and dioctyl maleate, fumaric acid alkyl esters such as
diethyl fumarate and dipropyl fumarate, citraconic acid alkyl
esters, mesaconic acid alkyl esters, allyl acetate.
[0093] Others: N-vinylcarbazole, maleimide, N-methylmaleimide,
vinylpyrrolidone, vinyl chloride.
[0094] The combination of the monomer units is preferably, in view
of the water/oil repellency and the wash durability, a combination
of monomer (a1): (meth)acrylate units having a C.sub.4-6 R.sup.F
group, monomer (a2): vinylidene chloride units and monomer (a3):
units of the monomer of the above-described preferred
embodiment.
[0095] The proportion of the monomer (a1) units is, in view of the
water/oil repellency and the wash durability, from 60 to 95 mass %,
preferably from 65 to 89.9 mass %, particularly preferably from 70
to 84.5 mass % relative to all the monomer units (100 mass %) in
the copolymer (A).
[0096] The proportion of the monomer (a2) units is, in view of the
water/oil repellency and the wash durability, from 5 to 40 mass %,
preferably from 10 to 34.9 mass %, particularly preferably from 15
to 29.5 mass % relative to all the monomer units (100 mass %) in
the copolymer (A).
[0097] The proportion of the monomer (a3) units is preferably from
10 to 35 mass %, and in view of the adhesion to the
moisture-permeable waterproofing film and the wash durability, more
preferably from 0.1 to 25 mass %, particularly preferably from 0.5
to 15 mass % relative to all the monomer units (100 mass %) in the
copolymer (A).
[0098] The proportion of the monomer (a4) units is preferably from
0 to 35 mass %, more preferably from 0 to 30 mass %, particularly
preferably from 0 to 15 mass % relative to all the monomer units
(100 mass %) in the copolymer (A).
[0099] The mass average molecular weight (Mw) of the copolymer (A)
is preferably at least 70,000, more preferably at least 75,000,
particularly preferably at least 80,000. Within such a range,
penetration of a coating liquid for formation of a
moisture-permeable waterproofing film or the like when applied to
the rear side of a porous substrate, to the front surface side, can
be suppressed. The mass average molecular weight (Mw) of the
copolymer (A) is preferably at most 200,000, particularly
preferably at most 170,000 in view of the film-forming property and
the storage stability.
[0100] The number average molecular weight (Mn) of the copolymer
(A) is preferably at least 32,000, particularly preferably at least
35,000. The number average molecular weight (Mn) of the copolymer
(A) is preferably at most 100,000, particularly preferably at most
80,000.
(Copolymer (B))
[0101] The copolymer (B) has units based on the monomer (b1) and
units based on the monomer (b2).
[0102] The copolymer (B) may have units based on the monomer (b3)
as the case requires.
Monomer (b1):
[0103] The monomer (b1) is a halogenated olefin.
[0104] By having the monomer (b1) units, the strength of the
coating film will be improved, and the adhesion to the substrate or
the moisture-permeable waterproofing film will be improved.
[0105] The halogenated olefin is preferably chlorinated olefin or
fluorinated olefin, and may, for example, be specifically vinyl
chloride, vinylidene chloride, tetrafluoroethylene or vinylidene
fluoride. In view of the adhesion to the substrate or the
moisture-permeable waterproofing film, more preferred is vinyl
chloride or vinylidene chloride, and particularly preferred is
vinyl chloride.
Monomer (b2):
[0106] The monomer (b2) is a monomer having no R.sup.f group and
having a crosslinkable functional group.
[0107] By having the monomer (b2) units, peeling of the
moisture-permeable waterproofing film will be suppressed. Further,
the wash durability of an article will further be improved.
[0108] The crosslinkable functional group may be the functional
groups exemplified for the monomer (a3), and the preferred
embodiment is also the same.
[0109] The monomer (b2) may be the compound exemplified for the
monomer (a3), and the preferred embodiment is also the same.
Monomer (b3):
[0110] The monomer (b3) is another monomer excluding the monomer
(b1) and the monomer (b2).
[0111] The monomer (b3) may be the compound exemplified for the
above monomer (a1) or the above monomer (a4).
[0112] The monomer (b3) is preferably the monomer (a1) or the
monomer (a4).
[0113] The copolymer (B) is, from the viewpoint of the
compatibility with the copolymer (A), preferably a copolymer (B)
having units based on the monomer (b3), at least part of the
monomer (b3) being the above monomer (a1).
[0114] The combination of the monomer units is, with a view to
suppressing peeling of the moisture-permeable waterproofing film,
preferably a combination of vinyl chloride units or vinylidene
chloride units as the monomer (b1) units, units of the monomer (b2)
and units of the monomer (b3) of the above preferred
embodiments.
[0115] The proportion of the monomer (b1) units is, with a view to
suppressing peeling of the moisture-permeable waterproofing film,
from 50 to 95 mass %, more preferably from 55 to 95 mass %,
particularly preferably from 55 to 90 mass % relative to all the
monomer units (100 mass %) in the copolymer (B).
[0116] The proportion of the monomer (b2) units is, with a view to
suppressing peeling of the moisture-permeable waterproofing film,
from 5 to 50 mass %, more preferably from 5 to 45 mass %,
particularly preferably from 5 to 25 mass % relative to all the
monomer units (100 mass %) in the copolymer (B).
[0117] The proportion of the monomer (b3) units is from 0 to 45
mass %, more preferably from 2 to 40 mass %, particularly
preferably from 5 to 35 mass % relative to all the monomer units
(100 mass %) in the copolymer (B).
[0118] The mass average molecular weight (Mw) of the copolymer (B)
is preferably at least 10,000, more preferably at least 20,000,
particularly preferably at least 30,000. Within the above range,
the obtainable article will be excellent in the water/oil
repellency and the wash durability. The mass average molecular
weight (Mw) of the copolymer (B) is, in view of the film-forming
property and the storage stability, preferably at most 1,000,000,
particularly preferably at most 500,000.
[0119] The number average molecular weight (Mn) of the copolymer
(B) is preferably at least 5,000, particularly preferably at least
10,000. The number average molecular weight (Mn) of the copolymer
(B) is preferably at most 300,000, particularly preferably at most
150,000.
(Method for Producing Copolymer)
[0120] The copolymer (A) and the copolymer (B) are produced, for
example, by a method of polymerizing the monomer components
including the above respective monomers in a medium in the presence
of a polymerization initiator to obtain a solution, dispersion or
emulsion of each copolymer.
[0121] The polymerization method may, for example, be a solution
polymerization method, a dispersion polymerization method, an
emulsion polymerization method or a suspension polymerization
method, and emulsion polymerization is preferred. Further, the
polymerization method may be polymerization all at once or
multistage polymerization.
[0122] The method for producing the copolymer (A) and the copolymer
(B) is preferably a method of polymerizing the monomer components
including the above respective monomers by emulsion polymerization
in an aqueous medium in the presence of a surfactant and a
polymerization initiator to obtain an emulsion of each
copolymer.
[0123] With a view to improving the yield of the copolymer, it is
preferred to pre-emulsify a mixture comprising the monomers, the
surfactant and the aqueous medium, prior to the emulsion
polymerization. For example a mixture comprising the monomers, the
surfactant and the aqueous medium is mixed and dispersed by an
ultrasonic stirring apparatus, a homomixer or a high pressure
emulsifier.
Polymerization Initiator:
[0124] The polymerization initiator may, for example, be a thermal
polymerization initiator, a photopolymerization initiator, a
radiation polymerization initiator, a radical polymerization
initiator or an ionic polymerization initiator, and a water-soluble
or oil-soluble radical polymerization initiator is preferred.
[0125] As the radical polymerization initiator, a common initiator
such as an azo type polymerization initiator, a peroxide type
polymerization initiator or a redox type initiator is employed
depending upon the polymerization temperature. As the radical
polymerization initiator, an azo type compound is particularly
preferred, and in a case where polymerization is carried out in an
aqueous medium, a salt of an azo type compound is more preferred.
The polymerization temperature is preferably from 20 to 150.degree.
C.
[0126] The amount of the polymerization initiator is preferably
from 0.1 to 5 parts by mass, more preferably from 0.1 to 3 parts by
mass, per 100 parts by mass of the monomer components.
Molecular Weight-Controlling Agent:
[0127] At the time of polymerization of the monomer components, a
molecular weight-controlling agent may be employed. The molecular
weight-controlling agent is preferably an aromatic compound, a
mercapto alcohol or a mercaptan, particularly preferably an
alkylmercaptan.
[0128] The amount of addition of the molecular weight-controlling
agent is properly adjusted so that Mw and Mn of the obtainable
copolymer will be within the above ranges.
Medium:
[0129] As the medium, the after-mentioned medium (C) may be
mentioned, and an aqueous medium is preferred.
[0130] The aqueous medium may be the same aqueous medium as
mentioned hereinafter, and the preferred embodiment is also the
same.
Surfactants:
[0131] The surfactant may be the after-mentioned surfactant (D),
and the preferred embodiment is also the same.
[0132] The proportion of the monomers in the monomer components is
the same as the proportion of the monomer units in the copolymer
since substantially 100% of the monomers are polymerized, and the
preferred embodiment is also the same.
[0133] The solid content concentration of the emulsion is
preferably from 20 to 40 mass % in the emulsion (100 mass %)
immediately after production of the copolymer. Further, the solid
content concentration is a concentration containing the surfactant
in addition to the copolymer. The content of the copolymer in the
emulsion is preferably from 18 to 40 mass % immediately after
production of the copolymer.
[0134] The solid content concentration of the emulsion is
calculated from the mass of the emulsion before heating and the
mass after drying for 4 hours by a counter current canal dryer at
120.degree. C.
(Medium (C))
[0135] The medium (C) may, for example, be water, an alcohol (such
as an alkanoyl, an alkylene glycol or a polyalkylene glycol), a
monoalkyl ether of a polyhydric alcohol, a halogen compound, a
hydrocarbon, a ketone, an ester, an ether, a nitrogen compound, a
sulfur compound, an inorganic solvent or an organic acid.
[0136] The alcohol is preferably an alkanoyl having at most 6
carbon atoms, a dihydric alcohol (such as an alkylene glycol)
having at most 4 carbon atoms, or a multimer of a dihydric alcohol
having at most 4 carbon atoms (such as dialkylene glycol or
trialkylene glycol). The monoalkyl ether of a polyhydric alcohol is
preferably a monoalkyl ether of an alkylene glycol having at most 4
carbon atoms or its multimer polyalkylene glycol, in which the
alkyl group has from 1 to 4 carbon atoms.
[0137] The medium (C) is preferably an aqueous medium in view of
the solubility and the handling efficiency.
[0138] The aqueous medium may be water or water containing a
water-soluble organic solvent.
[0139] The water-soluble organic solvent may, for example, be
tert-butanol, 3-methoxymethylbutanol, propylene glycol, dipropylene
glycol, dipropylene glycol monomethyl ether or tripropylene glycol,
and is preferably dipropylene glycol, tripropylene glycol or
dipropylene glycol monomethyl ether.
[0140] In a case where the aqueous medium contains the
water-soluble organic solvent, the content of the water-soluble
organic solvent is preferably from 1 to 80 parts by mass, more
preferably from 10 to 60 parts by mass per 100 parts by mass of
water.
(Surfactant (D))
[0141] The surfactant (D) may, for example, be a hydrocarbon type
surfactant or a fluorinated surfactant, and each of which may, for
example, be an anionic surfactant, a nonionic surfactant, a
cationic surfactant, or an amphoteric surfactant. As the surfactant
(D), from the viewpoint of the compatibility with additives, it is
preferred to use a nonionic surfactant and an amphoteric surfactant
in combination, and from the viewpoint of the adhesion, it is
preferred to use a nonionic surfactant alone or to use a nonionic
surfactant and a cationic surfactant in combination. The ratio of
the nonionic surfactant to the cationic surfactant (nonionic
surfactant/cationic surfactant) is preferably from 97/3 to 40/60
(mass ratio).
[0142] The nonionic surfactant is preferably at least one member
selected from the group consisting of surfactants s.sup.1 to
s.sup.6 as disclosed in Patent Documents 1 and 2.
[0143] In a case where the surfactant (D) contains a cationic
surfactant, such a cationic surfactant is preferably surfactant
s.sup.7 as disclosed in Patent Documents 1 and 2.
[0144] In a case where the surfactant (D) contains an amphoteric
surfactant, such an amphoteric surfactant is preferably surfactant
s.sup.8 as disclosed in Patent Documents 1 and 2.
[0145] Further, as the surfactant (D), surfactant S.sup.9 (polymer
surfactant) as disclosed in Patent Documents 1 and 2 may also be
used.
[0146] The preferred embodiment of the surfactant (D) is the same
as the preferred embodiment disclosed in Patent Documents 1 and
2.
(Additives (E))
[0147] The additives include, for example, a penetrant, a defoamer,
a water-absorbing agent, an antistatic agent, an antistatic
polymer, an anticrease agent, a texture-adjusting agent, a
film-forming assistant, a water-soluble polymer (such as
polyacrylamide or polyvinyl alcohol), a thermosetting agent (such
as a melamine resin, a urethane resin, a triazine ring-containing
compound or an isocyanate-type compound), an epoxy curing agent
(such as isophthalic acid dihydrazide, adipic acid dihydrazide,
sebacic acid dihydrazide, dodecanedioic acid dihydrazide,
1,6-hexamethylenebis(N,N-dimethylsemicarbazide),
1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide
or spiroglycol), a thermosetting catalyst, a crosslinking catalyst
(such as an organic acid or ammonium chloride), a synthetic resin,
a fiber-stabilizer and inorganic fine particles.
[0148] Further, the water/oil repellent composition of the present
invention may contain a copolymer capable of exhibiting water
repellency and/or oil repellency (e.g. a commercially available
water repellent, a commercially available oil repellent, a
commercially available water/oil repellent or a commercially
available SR (soil release) agent) other than the copolymer (A) and
the copolymer (B), a water-repellent compound having no fluorine
atom, or the like as the case requires. The water-repellent
compound having no fluorine atom may, for example, be a paraffin
type compound, an aliphatic amide type compound, an alkylethylene
urea compound or a silicone compound.
(Proportion of Components in Water/Oil Repellent Composition)
[0149] The proportion of the copolymer (A) is from 70 to 90 mass %,
preferably from 75 to 90 mass %, particularly preferably from 81 to
90 mass % relative to the total amount (100 mass %) of the
copolymer (A) and the copolymer (B). When the proportion of the
copolymer (A) is at least 70 mass %, the water/oil repellency and
the wash durability are favorable, and penetration of the coating
liquid for formation of the moisture-permeable waterproofing film
can be suppressed. When the proportion of the copolymer (A) is at
most 90 mass %, peeling of the moisture-permeable waterproofing
film can be suppressed.
[0150] The proportion of the copolymer (B) is from 10 to 30 mass %,
preferably from 10 to 25 mass %, particularly preferably from 10 to
19 mass % relative to the total amount (100 mass %) of the
copolymer (A) and the copolymer (B). When the proportion of the
copolymer (B) is at least 10 mass %, peeling of the
moisture-permeable waterproofing film can be suppressed. When the
proportion of the copolymer (B) is at most 30 mass %, the water/oil
repellency and the wash durability will be favorable, and
penetration of the coating liquid for formation of the
moisture-permeable waterproofing film can be suppressed.
[0151] The amount of the surfactant (D) is preferably from 1 to 10
parts by mass, more preferably from 1 to 9 parts by mass,
particularly preferably from 1 to 7 parts by mass relative to the
total amount (100 parts by mass) of the copolymer (A) and the
copolymer (B).
[0152] The solid content concentration of the water/oil repellent
composition of the present invention is preferably from 0.2 to 5
mass % in the water/oil repellent composition (100 mass %) at the
time of treating the substrate.
[0153] The solid content concentration of the water/oil repellent
composition is calculated from the mass of the water/oil repellent
composition before heating and the mass after drying for 4 hours by
a counter current canal dryer at 120.degree. C.
(Average Particle Size)
[0154] In the water/oil repellent composition of the present
invention, it is preferred that the copolymer is dispersed in the
form of particles in the aqueous medium.
[0155] The average particle size of the copolymer is preferably
from 10 to 1,000 nm, more preferably from 10 to 300 nm,
particularly preferably from 10 to 250 nm. When the average
particle size is within such a range, it will be unnecessary to use
a surfactant, etc. in a large amount, the water repellency will be
good, and when dyed cloths are treated, no color fading will
result, and the dispersed particles can stably be present in the
aqueous medium without precipitation. The average particle size of
the copolymer can be measured by e.g. a dynamic light-scattering
apparatus or an electron microscope.
(Functional Effect)
[0156] The above-described water/oil repellent composition of the
present invention comprises a copolymer (A) having from 60 to 95
mass % of the monomer (a1) units and from 5 to 40 mass % of the
monomer (a2) units in a specific proportion, and accordingly by
using such a composition, it is possible to obtain a porous
substrate which has favorable water/oil repellency and wash
durability, and through which penetration of the coating liquid for
formation of a moisture-permeable waterproofing film is
suppressed.
[0157] Further, the water/oil repellent composition of the present
invention comprises a copolymer (B) having from 50 to 95 mass % of
the monomer (b1) units and from 5 to 50 mass % of the monomer (b2)
units in a specific proportion, and accordingly by using such a
composition, it is possible to obtain an article from which peeling
of the moisture-permeable waterproofing film is suppressed.
[0158] Further, in the water/oil repellent composition of the
present invention, the copolymer (A) nor the copolymer (B) has
units of a monomer having an R.sup.F group having at least 7 carbon
atoms, whereby the content (content in a case where the solid
content concentration is 20 mass %) of perfluorooctanoic acid
(PFOA) and perfluorooctanesulfonic acid (PFOS), and their
precursors and analogues of which the effects on the environment
are pointed out, can be reduced to a level of not higher than the
detection limit as an analytical value of LC-MS/MS by the method
disclosed in WO2009/081822.
(Application)
[0159] The water/oil repellent composition of the present invention
may be used for treating the surface of a substrate. Further, it is
also useful to applications to impart water/oil repellency by
mixing with polypropylene, nylon or the like, followed by forming
and formation into fibers.
[0160] The substrate to be treated may, for example, be fibers
(natural fibers, synthetic fibers, mixed fibers, etc.), cloths
(woven fabric, textile fabric, nonwoven fabric, etc.), various
fiber products (clothing (sports wears, coats, jumpers, work
clothes, uniforms, etc.), bags, industrial materials, etc.), resin
products, paper, leathers, metal products, stone products, concrete
products, gypsum products and glass products.
[0161] The substrate is preferably a porous substrate. The porous
substrates includes cloths (woven fabric, textile fabric, nonwoven
fabric, etc.), porous fiber products such as clothing, a porous
resin sheet, pumice and wood. Particularly, cloths are
preferred.
[0162] The treatment method may, for example, be a method of
coating the substrate with a coating liquid containing the
water/oil repellent composition by a known coating method, followed
by drying, or a method of dipping the substrate in a coating liquid
containing the water/oil repellent composition, followed by
drying.
[0163] Further, after treatment with the water/oil repellent
composition of the present invention, antistatic finish, softening
finish, antibacterial finish, deodorant finish or waterproofing
finish may, for example, be carried out.
<Article>
[0164] The present invention provides an article which has a porous
substrate having a water/oil repellent-treated surface treated with
the water/oil repellent composition on one side, and a
moisture-permeable waterproofing film on one side. It may, for
example, be cloth having a water/oil repellent-treated surface on
one side and having a moisture-permeable waterproofing film on the
other side not water/oil repellent-treated, or a clothing obtained
by using such cloth. Further, it may also be cloth having water/oil
repellent-treated surfaces on both sides and having a
moisture-permeable waterproofing film on one water/oil
repellent-treated surface, or a clothing obtained by using such
cloth.
[0165] The moisture-permeable waterproofing film may, for example,
be a porous polyurethane resin film.
[0166] The present invention further provides a method for
producing a porous substrate having a water/oil repellent-treated
surface and a moisture-permeable waterproofing film, which
comprises treating at least one side of a porous substrate with the
water/oil repellent composition to form the water/oil
repellent-treated surface, and applying a coating liquid containing
a material of the moisture-permeable waterproofing film to one side
of the porous substrate to form the moisture-permeable
waterproofing film.
[0167] Specifically, for example, a porous substrate having a
water/oil repellent-treated surface and a moisture-permeable
waterproofing film is produced by a method of subjecting one side
of the porous substrate to water/oil repellent treatment and then
forming the moisture-permeable waterproofing film to a side not
water/oil repellent-treated, or a method of subjecting both sides
of the porous substrate to water/oil repellent treatment, and
forming the moisture-permeable waterproofing film to one of the
water/oil repellent-treated surfaces.
[0168] The porous substrate is preferably cloth, and the
moisture-permeable waterproofing film is preferably a microporous
polyurethane resin film.
[0169] The coating liquid contains a material of the
moisture-permeable waterproofing film, the solvent and the
like.
[0170] The material of the moisture-permeable waterproofing film
may be a known polyurethane resin obtainable by reacting a
polyisocyanate component and a polyol component. As the
polyisocyanate component, an aromatic diisocyanate, an aliphatic
diisocyanate, an alicyclic diisocyanate and the like may be used
alone or as mixed. Specifically, tolylene-2,4-diisocyanate,
4,4'-diphenylmethanediisocyanate, 1,6-hexanediisocyanate,
1,4-cyclohexanediisocyanate or the like may be used as the main
component, and as the case requires, a tri-functional or higher
polyisocyanate may be used. As the polyol component, a polyether
polyol, a polyester polyol or the like may be used. As the
polyether polyol, polyethylene glycol, polypropylene glycol,
polytetraethylene glycol or the like may be used. As the polyester
polyol, a reaction product of a diol such as ethylene glycol or
propylene glycol and a dibasic acid such as adipic acid or sebacic
acid, or a ring-opening polymer of e.g. caprolactone may be used,
and needless to say, a polymer of an oxyacid monomer or a
prepolymer thereof may be used.
[0171] As the solvent, a polar organic solvent is preferably used,
and N,N-dimethylformamide (DMF), N,N-dimethylacetamide,
dimethylsulfoxide, N-methylpyrrolidone or
hexamethylenephosphonamide may, for example, be mentioned. An
assistant such as a fluorinated water repellent or crosslinking
agent may be added to the polyurethane resin solution.
[0172] The moisture-permeable waterproofing film may be formed, for
example, by applying the coating liquid to one surface of the
porous substrate, leaving the porous substrate at rest for a
certain time, and then dipping the substrate in water for a
predetermined time to remove the solvent, followed by drying. As
the coating method, various coating methods such as knife coating,
knife over roll coating and reverse roll coating may be
employed.
[0173] By the above-described method for producing the porous
substrate of the present invention, it is possible to obtain a
porous substrate having a water/oil repellent-treated surface and a
moisture-permeable waterproofing film, which has favorable
water/oil repellency and wash durability, which is excellent in the
design since penetration of the coating liquid for formation of the
moisture-permeable waterproofing film or the like is suppressed,
from which the moisture-permeable waterproofing film is hardly
peeled, and which presents a low environmental impact.
Examples
[0174] Now, the present invention will be described in detail with
reference to Examples. However, it should be understood that the
present invention is by no means restricted thereto.
[0175] Ex. 1 to 13 are Preparation Examples, Ex. 15, 22 to 26, 28
to 30 and 32 to 37 are Examples of the present invention, and Ex.
14, 16 to 21, 27 and 31 are Comparative Examples.
<Physical Properties of Copolymer>
[0176] With respect to a copolymer recovered by the following
recovering method, the molecular weight was measured.
(Recovering Method)
[0177] 6 g of an emulsion was dropped to 60 g of 2-propanol
(hereinafter referred to as IPA), followed by stirring to
precipitate a solid. The mixture was subjected to centrifugal
separation at 3,000 rpm for 5 minutes, and the obtained solid was
separated. 12 g of IPA was added again, followed by stirring. The
mixture was subjected to centrifugal separation at 3,000 rpm for 5
minutes, and the obtained solid was separated from the supernatant
liquid and vacuum dried at 35.degree. C. overnight to obtain a
copolymer.
(Molecular Weight)
[0178] The recovered copolymer was dissolved in a solvent mixture
of a fluorinated solvent (AK-225 manufactured by Asahi Glass
Company, Limited)/THF=6/4 (volume ratio) to form a 0.5 mass %
solution, which was passed through a 0.2 .mu.m filter to prepare a
sample for analysis. With respect to the sample, the number average
molecular weight (Mn) and the mass average molecular weight (Mw)
were measured. The measuring conditions are as follows.
[0179] Apparatus: HLC-8220 GPC manufactured by Tosoh
Corporation,
[0180] Column: MIXED-C and 100A manufactured by Polymer
Laboratories connected in series,
[0181] Measurement temperature: 37.degree. C.,
[0182] injected amount: 50 .mu.L,
[0183] outflow rate: 1 .mu.L/min,
[0184] standard sample: EasiCal PS-2 manufactured by Polymer
Laboratories,
[0185] eluent: a solvent mixture of a fluorinated solvent (AK-225
manufactured by Asahi Glass Company, Limited)/THF=6/4 (volume
ratio).
<Evaluation of Treated Cloth>
(Water Repellency)
[0186] With respect to a test cloth, the water repellency was
evaluated in accordance with the spray test in JIS L1092-1998. The
water repellency is represented by five grades of from 1 to 5. The
higher the grade number, the better the water repellency. A test
cloth with a grade 3 or higher is considered to have water
repellency. A grade having +(-) attached shows that the property is
slightly better (worse) than the standard property of that
grade.
(Wash Durability)
[0187] With respect to a test cloth, washing was repeated 20 times
or 50 times in accordance with water washing method in JIS L 0217
appendix 103. After washing, the test cloth was air-dried in a room
at a temperature of 25.degree. C. under a humidity of 60%
overnight, whereupon the water repellency was evaluated as
described above.
(Oil Repellency)
[0188] With respect to a test cloth, the oil repellency was
evaluated in accordance with the test method in AATCC-TM118-1966.
The oil repellency is represented by the grades as shown in Table
1. A grade having +(-) attached shows that the property is slight
better (worse) than the standard property of that grade.
TABLE-US-00001 TABLE 1 Oil repellency Surface tension (25.degree.
C.) No. Test solution [mN/m] 8 n-Heptane 20.0 7 n-Octane 21.8 6
n-Decane 23.5 5 n-Dodecane 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane
27.3 2 65 Parts of nujol/ 29.6 35 parts of hexadecane 1 Nujol 31.2
0 Less than 1 --
(Wash Durability)
[0189] With respect to a test cloth, washing was repeated 20 times
in accordance with water washing method in JIS L 0217 appendix 103.
After washing, the test cloth was air-dried in a room at a
temperature of 25.degree. C. under a humidity of 60% overnight,
whereupon the oil repellency was evaluated as described above.
(Penetration of Coating Liquid)
[0190] Using a colorimeter (CR310 manufactured by KONICA MINOLTA,
INC.), before a moisture-permeable waterproofing film was formed,
the brightness of the surface of a test cloth on a side on which a
moisture-permeable waterproofing film would not be to be formed,
was measured, and after a moisture-permeable waterproofing film was
formed, the brightness of the surface of the test cloth on the side
on which the moisture-permeable waterproofing film was not formed,
was measured, and their reference (.DELTA.L) was obtained.
(Peel Strength)
[0191] A heat seal tape was attached to the moisture-permeable
waterproofing film of a test cloth by hot press. Using a Tensilon
universal testing machine (AGS-X manufactured by Shimadzu
Corporation), a force (peel strength) applied when a 2.5 cm of the
tape was peeled was measured. Measurement was carried out three
times in total, and the average of the peel strengths was obtained.
The higher the peel strength, the less the moisture-permeable
waterproofing film formed by the coating liquid is likely to be
peeled.
<Abbreviations>
(Monomer)
[0192] CmFA: F(CF.sub.2).sub.mCH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2
(a mixture of compounds wherein m is from 6 to 16, at least 99 mass
% thereof are compounds wherein m is 8 or higher, and the average
of m is 9),
[0193] FMA:
F(CF.sub.2).sub.6CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.sub.2,
[0194] VCM: vinyl chloride,
[0195] VDC: vinylidene chloride,
[0196] STA: stearyl acrylate,
[0197] BeA: behenyl acrylate,
[0198] BMA: n-butyl methacrylate,
[0199] MMA: methyl methacrylate
[0200] CHMA: cyclohexyl methacrylate,
[0201] DOM: dioctyl maleate,
[0202] D-BI: 3,5-dimethylpyrazole adduct of 2-isocyanateethyl
methacrylate,
[0203] NMAM: N-methylolacrylamide,
[0204] HEMA: 2-hydroxyethyl methacrylate,
[0205] GMA: glycidyl methacrylate.
(Surfactant (D))
[0206] PEO-20: a 10 mass % aqueous solution of polyoxyethylene
oleyl ether (ethylene oxide about 26 mol adduct) (Emulgen E430
manufactured by Kao Corporation),
[0207] PEO-13: 10 mass % aqueous solution of polyoxyethylene oleyl
ether (ethylene oxide about 13 mol adduct) (Emulgen E420
manufactured by Kao Corporation),
[0208] SFY: 10 mass % aqueous solution of
2,4,7,9-tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (30
mols of ethylene oxide added) (Surfynol 485 manufactured by Nissin
Chemical Industry Co., Ltd.),
[0209] P204: 10% aqueous solution of ethylene oxide propylene oxide
polymer (containing 40 mass % of ethylene oxide) (PRONONE 204
manufactured by NOF Corporation)
[0210] AM3130: a 10 mass % aqueous solution of coconut oil fatty
acid amidepropyldimethylaminoacetic acid betain,
[0211] AM301: a 10 mass % aqueous solution of lauryl
dimethylaminoacetic acid betain,
[0212] TMAC: a 10 mass % aqueous solution of tirmethylammonium
chloride (ARQUAD 18-63 manufactured by Lion Corporation).
(Medium (C))
[0213] DPG: dipropylene glycol
[0214] Water: deionized water
(Molecular Weight-Controlling Agent)
[0215] nDoSH: n-dodecylmercaptan,
[0216] StSH: Stearyl mercaptan
(Polymerization Initiator)
[0217] VA061A: a 10 mass % aqueous solution of
2,2'-azobis[2-(2-imidazolin-2-yl)propane]acetate,
[0218] V-50: a 10 mass % aqueous solution of
2,2'-azobis(2-methylpropionamidine)dihydrochloride.
(Additives)
[0219] KB1000: silicone softening agent (HISOFTER KB1000
manufactured by Meisei Chemical Works, Ltd.),
[0220] DP9C: blocked isocyanate (Trixene DP9C/214 manufactured by
Baxenden),
[0221] TP-10: blocked isocyanate (MEIKANATE TP-10 manufactured by
Meisei Chemical Works, Ltd.),
[0222] M-3: melamine resin (BECKAMINE M-3 manufactured by DIC
Corporation),
[0223] ACX: crosslinking catalyst (ACCELERATOR ACX manufactured by
DIC Corporation).
Preparation of Copolymer
Copolymer (A)
Ex. 1
[0224] 218 g of FMA, 3 g of HEMA, 109 g of PEO-13, 96 g of AM3130,
82 g of DPG, 239 g of water and 0.3 g of StSH were put into a glass
beaker, heated at 60.degree. C. for 30 minutes, and then mixed by a
homomixer (BIO MIXER manufactured by Nihonseiki Kaisha, Ltd.) to
obtain a mixture.
[0225] The mixture was treated by a high-pressure emulsification
equipment (Mini-Lab manufactured by APV Ranie) at 60.degree. C.
under 40 MPa to obtain an emulsion. The obtained emulsion was put
into a stainless steel reactor and cooled to 40.degree. C. or
below. 1.3 g of V-50 was added, the gas phase was replaced with
nitrogen, and 49 g of VDC was introduced, and then the reaction
mixture was heated to 60.degree. C. for 15 hours with stirring to
carry out a polymerization reaction to obtain an emulsion of
copolymer (A-1). The solid content was 36.1 mass %. The amounts of
the materials charged are shown in Table 2. The proportion of the
monomer units, the amount of addition of the molecular
weight-controlling agent and the molecular weight are shown in
Table 3.
TABLE-US-00002 TABLE 2 Amount charged (g) Ex. 1 FMA 218 STA BeA BMA
MMA CHMA DOM D-BI NMAM HEMA 3 GMA PEO-20 PEO-13 109 SFY P204 AM3130
96 AM301 TMAC DPG 82 Water 239 nDoSH StSH 0.3 Amount of emulsion
charged (g) 699.7 VCM VDC 49 VA061A V-50 1.3 Solid content (mass %)
36.9 Copolymer A-1
TABLE-US-00003 TABLE 3 Monomer units (mass %) Ex. 1 FMA 80 VCM VDC
19 STA BeA BMA CHMA DOM D-BI NMAM HEMA 1 GMA nDoSH StSH 0.1 Mn
38,000 Mw 140,000 Copolymer A-1
Copolymer (B)
Ex. 2 to 13
[0226] Emulsions of copolymers (B-1) to (B-3), (B'-4) to (B'-5),
(B-6) to (B-9) and (B'-10) to (B'-12) were obtained in the same as
in Ex. 1 except that the amounts of materials charged were changed
as identified in Table 4. The timing of addition of VCM was the
same as that of VDC. The amounts of the materials charged are shown
in Table 4. The proportion of the monomer units and the amount of
addition of the molecular weight-controlling agent are shown in
Table 5.
TABLE-US-00004 TABLE 4 Amount charged Ex. (g) 2 3 4 5 6 7 FMA 4 2 4
115 110 5 STA BeA BMA 22 MMA CHMA 77 69 DOM D-BI 3 2 3 4 NMAM HEMA
3 2 3 4 GMA 11 6 11 82 69 PEO-20 54 54 110 110 54 PEO-13 24 SFY
P204 27 27 AM3130 14 14 AM301 21 TMAC 16 16 16 DPG 33 18 33 82 82
33 Water 587 677 587 290 290 587 nDoSH StSH 0.5 0.3 0.5 1.1 1.1 0.5
Amount of 668.5 704.7 688.5 749.2 723.2 659.5 emulsion charged (g)
VCM 81 61 26 90 VDC 45 VA061A 0.5 0.3 0.5 0.8 0.8 0.5 V-50 Solid
content 14.6 8.1 14.6 36.5 36.5 14.6 (mass %) Copolymer B-1 B-2 B-3
B'-4 B'-5 B-6 Amount charged Ex. (g) 8 9 10 11 12 13 FMA 4 5 203 47
138 STA 19 127 BeA 158 BMA MMA CHMA DOM 11 D-BI 3 11 6 NMAM 4 6
HEMA 3 3 4 3 GMA 11 11 PEO-20 54 54 54 85 83 PEO-13 SFY 83 P204 25
14 AM3130 AM301 TMAC 16 16 16 25 14 28 DPG 33 33 33 82 83 83 Water
587 587 587 304 328 328 nDoSH 2.7 2.8 2.1 StSH 0.5 0.5 0.5 Amount
of 664.5 665.5 659.5 709.7 696.3 749.3 emulsion charged (g) VCM 85
84 90 39 53 VDC VA061A 0.5 0.5 0.5 1.3 0.7 0.7 V-50 Solid content
14.6 14.6 14.6 36.5 36.3 36.2 (mass %) Copolymer B-7 B-8 B-9 B'-10
B'-11 B'-12
TABLE-US-00005 TABLE 5 Monomer units Ex. (mass %) 2 3 4 5 6 7 8 9
10 11 12 13 FMA 4 4 4 42 40 5 4 4 74 17 50 VCM 80 60 10 88.4 83.4
82.6 89.4 15 20.5 VDC 80 STA 7 46 BeA 57.5 BMA 20 CHMA 28 25 DOM 4
D-BI 3 3 3 3.3 3.1 4 2 NMAM 3.3 2 HEMA 3 3 3 3.3 3.1 3.1 3.3 1 GMA
10 10 10 30 25 10.4 10.3 nDoSH 1 1 0.75 StSH 0.5 0.5 0.5 0.4 0.4
0.5 0.5 0.5 0.5 Copolymer B-1 B-2 B-3 B'-4 B'-5 B-6 B-7 B-8 B-9
B'-10 B'-11 B'-12
Preparation of Water/Oil Repellent Composition and Treatment of
Cloth
Ex. 14 to 17
[0227] The emulsion of the copolymer (A) and the emulsion of the
copolymer (B) as shown in Table 6 were mixed in a mass ratio as
shown in Table 6 and diluted with water to adjust the solid content
concentration to be 1.2 mass %, and additives as shown in Table 6
were added at concentrations shown in Table 6 to obtain a water/oil
repellent composition.
[0228] A base cloth (nylon high density taffeta) was dipped in the
water/oil repellent composition by a padding method and nipped to a
wet pick-up of 52 mass %. The cloth was dried at 110.degree. C. for
90 seconds and at 170.degree. C. for 60 seconds, and left in a room
at 25.degree. C. under a humidity of 60% overnight to obtain a test
cloth.
[0229] 50 g of RESAMINE CU-4700 (manufactured by Dainichiseika
Color & Chemicals Mfg. Co., Ltd., urethane prepolymer), 0.5 g
of CORONATE HL (manufactured by Nippon Polyurethane Industry Co.,
Ltd.), 1.0 g of SEIKASEVEN ALT #8000 (manufactured by Dainichiseika
Color & Chemicals Mfg. Co., Ltd.) and 25 g of DMF were mixed to
obtain a coating liquid.
[0230] The coating liquid was applied to the rear side of the test
cloth using an applicator (RK Print Coat Instruments Ltd.) under
conditions of a coating rate of 0.1 m/sec and a coating liquid
temperature of 35.degree. C. so that the thickness after drying
would be 40 .mu.m. The coated test cloth was left at rest for 1
minute, dipping in water at 20.degree. C. for 2 minutes and then
dipped in water at 40.degree. C. for 2 minutes, and dried at
120.degree. C. for 60 seconds to prepare a test cloth with a
moisture-permeable waterproofing film. This test cloth was
evaluated. The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Ex. 14 15 16 17 Copolymer Type A-1 A-1 A-1
A-1 (A) (mass %) 100 80 80 80 Copolymer Type B-1 B'-5 B'-4 (B)
(mass %) 20 20 20 Additives KB1000 (mass %) DP9C 0.5 0.5 0.5 0.5
TP-10 M-3 0.3 0.3 0.3 0.3 ACX 0.3 0.3 0.3 0.3 Water Initial 5 5 5 5
repellency Wash 20 4 3+ 4 4 times Wash 50 3++ 3+ 3++ 3++ times Oil
Initial 3- 3 3 3 repellency Wash 20 2 2+ 2+ 2+ times Coating
Penetration 0.5 0.5 0.5 0.4 applicability (.DELTA.L) Peel 6 8 4
<1 strength (N)
[0231] Ex. 14 to 17 are Examples to show the effect by addition of
the copolymer (B) to the copolymer (A). From the results in Ex. 14
and 15, it is found that the peel strength of the
moisture-permeable waterproofing film is increased when the
copolymer (B) within the range of the present invention is added to
the copolymer (A). From the results in Ex. 16 and 17, it is found
that the peel strength of the moisture-permeable waterproofing film
is decreased if the copolymer (B') out of the range of the present
invention is added to the copolymer (A).
Ex. 18 to 26
[0232] The emulsion of the copolymer (A) and the emulsion of the
copolymer (B) as shown in Table 7 were mixed in a mass ratio as
shown in Table 7 and diluted with water to adjust the solid content
concentration to be 1.2 mass %, and additives as shown in Table 7
are added at concentrations as shown in Table 7 to obtain a
water/oil repellent composition.
[0233] In the same manner as in Ex. 14 to 17, a base cloth (nylon
high density taffeta) was treated with the water/oil repellent
composition to obtain a test cloth.
[0234] In Ex. 18 to 21, a test cloth with a moisture-permeable
waterproofing film was obtained in the same manner as in Ex. 14 to
17. Further, in Ex. 22 to 26, a test cloth with a
moisture-permeable waterproofing film was obtained in the same
manner as in Ex. 14 to 17 except that the coated test cloth was
left at rest for 5 minutes. The obtained test cloths were
evaluated. The results are shown in Table 7.
TABLE-US-00007 TABLE 7 Ex. 18 19 20 21 22 23 24 25 26 Copolymer
Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 (A) (mass %) 100 80 80 80
80 80 80 80 80 Copolymer Type B'-10 B'-11 B'-12 B-1 B-6 B-7 B-8 B-9
(B) (mass %) 20 20 20 20 20 20 20 20 Additives KB1000 1.5 1.5 1.5
1.5 1.5 1.5 1.5 1.5 1.5 (mass %) DP9C 0.5 0.5 0.5 0.5 0.5 0.5 0.5
0.5 0.5 TP-10 M-3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ACX 0.3 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.3 Water Initial 4+ 4+ 4+ 4+ 4+ 4+ 4+ 4+
4+ repellency Wash 20 3 3 3 2+ 3 3 3 3+ 3+ times Wash 50 3 2 2 2 3-
3- 3- 3 3 times Oil Initial 3- 3 2 2 3- 3- 3- 3- 3- repellency Wash
20 2- 2- 1 1 2- 2- 2- 1+ 1+ times Coating Penetration 0.9 0.7 1.1
0.7 1.6 1.4 1.2 1.3 1.1 applicability (.DELTA.L) Peel 3 5 3 2 7 7 7
7 7 strength (N)
[0235] Ex. 18 is an Example in which the copolymer (A) was used
alone.
[0236] Ex. 19 to 21 are Examples in which a known water/oil
repellent which presents a low environmental impact was added to
the copolymer (A). From the results in Ex. 18 to 21, it is found
that the peel strength of the moisture-permeable waterproofing film
is not significantly improved even if each of copolymers (B'-10) to
(B'-12) which are known water/oil repellents is added.
[0237] Ex. 22 to 26 are Examples to show the effect by addition of
the copolymer (B) to the copolymer (A). From the results in Ex. 22
to 26, it is found that when the copolymer (B) within the range of
the present invention is added to the copolymer (A), penetration of
the coating liquid is slightly increased due to influence by the
long time for leaving the coated test cloth at rest, however the
peel strength of the moisture-permeable waterproofing film is
increased.
Ex. 27 to 37
[0238] The emulsion of the copolymer (A) and the emulsion of the
copolymer (B) as shown in Table 8 or 9 were mixed in a mass ratio
as shown in Table 8 or 9 and diluted with water to adjust the solid
content concentration to be 1.2 mass %, and additives as shown in
Table 8 or 9 were added at concentrations as shown in Table 8 or 9
to obtain a water/oil repellent composition.
[0239] In the same manner as in Ex. 14 to 17, a base cloth (nylon
high density taffeta) was treated with the water/oil repellent
composition to obtain a test cloth.
[0240] A test cloth with a moisture-permeable waterproofing film
was obtained in the same manner as in Ex. 14 to 17 except that the
thickness after drying was 10 .mu.m, and the coated test cloth was
left at rest for 5 minutes. The obtained test cloths were
evaluated. The results are shown in Tables 8 and 9.
TABLE-US-00008 TABLE 8 Ex. 27 28 29 30 31 32 33 34 Copolymer Type
A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 (A) (mass %) 100 90 80 70 60 90 80
70 Copolymer Type B-1 B-1 B-1 B-1 B-2 B-2 B-2 (B) (mass %) 10 20 30
40 10 20 30 Additives KB1000 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (mass
%) DP9C TP-10 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 M-3 0.3 0.3 0.3 0.3
0.3 0.3 0.3 0.3 ACX 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Water Initial
4+ 5- 5- 4+ 4+ 4+ 4+ 5- repellency Wash 20 4 4 4 3+ 2 4 4 4 times
Wash 50 3+ 3+ 3+ 3 2 3+ 3+ 3 times Oil Initial 3- 3- 2+ 2+ 2 2+ 2+
2+ repellency Wash 20 2 2+ 2 1+ 1- 1+ 2- 2- times Coating
Penetration 2.6 2.5 2.5 2.9 3.4 2.1 2.1 2.2 applicability
(.DELTA.L) Peel 3 6 6 6 7 6 5 5 strength (N)
TABLE-US-00009 TABLE 9 Ex. 27 35 36 37 Copolymer Type A-1 A-1 A-1
A-1 (A) (mass %) 100 90 80 70 Copolymer Type B-3 B-3 B-3 (B) (mass
%) 10 20 30 Additives KB1000 1.5 1.5 1.5 1.5 (mass %) DP9C TP-10
0.5 0.5 0.5 0.5 M-3 0.3 0.3 0.3 0.3 ACX 0.3 0.3 0.3 0.3 Water
Initial 4+ 5- 5- 4+ repellency Wash 20 4 4 3+ 3+ times Wash 50 3+
3+ 3 3 times Oil Initial 3- 2+ 2+ 2 repellency Wash 20 2 1+ 2 2-
times Coating Penetration 2.6 2.4 2.4 2.6 applicability (.DELTA.L)
Peel 3 6 5 6 strength (N)
[0241] Ex. 27 is an Example in which the copolymer (A) was used
alone.
[0242] Ex. 28 to 37 are Examples in which the mass ratio of the
copolymer (A) to the copolymer (B) was changed. From the results in
Ex. 28 to 37, it is found that the balance between suppression of
penetration of the coating liquid and the peel strength of the
moisture-permeable waterproofing film is favorable within a range
of the proportion of the copolymer (A) being from 70 to 90 mass %
and the proportion of the copolymer (B) being from 10 to 30 mass
%.
INDUSTRIAL APPLICABILITY
[0243] The water/oil repellent composition of the present invention
is useful as a water/oil repellent for e.g. cloth (woven fabric,
textile fabric, nonwoven fabric, etc.), various fiber products
(clothing (sports wears, coats, jumpers, work clothes, uniforms,
etc.), bags, industrial materials, etc.).
[0244] This application is a continuation of PCT Application No.
PCT/JP2013/070512 filed on Jul. 29, 2013, which is based upon and
claims the benefit of priority from Japanese Patent Application No.
2012-171133 filed on Aug. 1, 2012. The contents of those
applications are incorporated herein by reference in their
entireties.
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